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    M7180-DS intro 9-8 JLG to Mediasense-v12sk

    Classified - Internal Use Only

    TEKNOLOGI MINYAK,

    OLEOKIMIA DAN EMULSI

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    MATERI KULIAH :

    1. TEKNOLOGI MINYAK DAN LEMAK

    o Perkembangan teknologi, definisi & sumber minyak/lemak

    o

    Reaksi dalam minyak/lemako Sifat fisiko kimia minyak/lemak

    o Kerusakan minyak/lemak

    o Ekstraksi dan pemurnian minyak/lemak

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    2. TEKNOLOGI OLEOKIMIA

    3. TEKNOLOGI EMULSI

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    The Importance of Fats/Oils

    a. High content of energy (the greatest possible storage of energy in the

    smallest possible amount of food substance)

    b. Allow human to consume fat soluble-vitamins and provide essential

    fatty acids

    c. Provide a smooth, creamy consistency to many dishes (good mouth-

    feel)

    d. Economic aspect (> 90 mill ton of oils and fats).national interest- 60 mill ton of palm fruit

    - 11 mill ton of olives

    - > 200 mill of oil seeds

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    e. Substantial market for technical fats

    Oil type and non food usage (%)

    - Soybean oil 0.25

    - Palm oil 10- Palm kernel oil 10

    - Rapeseed oil 40

    - Coconut oil 55

    - Castor oil 100

    - Linseed oil 100

    - Tung oil 100

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    Type of usage (% of total non food usage)

    - Fatty acids 36

    - Animal feed 29

    - Soap 15- Other 13

    - Paints 3

    - Lubricants 2

    - Polymers 2

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    Comparison of Diesel oil, rapeseed oil and sunflower oil

    Sunflower Rapeseed

    Diesel oil Crude oil Methyl ester Crude oil Methyl ester

    1. Caloric value (MJ/kg) 42-46 39.28 40.16 37 37.02-37.20

    2. Density (g/cm3) 0.835 0.925 0.880 0.92 0.86-0.90

    3. Viscosity (cP, 20oC) 3.9 34.7 4.22 68-97 6-9

    4. Flash point (oC) 50-77 215.5 183 317-324 111-175

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    Energy balance from renewable sourcesSource Energy balance invested/yielded Energy yield net (GJ/ha)

    Sunflower oil 2.8 43.3

    Rapeseed oil 2.7 37.9

    Ethanol (sugar beet) 2.5 58.9Corn 1.3 18.4

    Wheat 1.1 5.2

    Requirements for fuel esters

    FFA < 0.2%

    Mono, diglycerides < 0.1%

    Glycerol < 0.1%

    Methanol < 0.2%

    Water < 0.1%

    Metals (each) < 5 ppm

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    Components of fats and oils

    Fats/Oils : esters of fatty acids with the trihydric alcohol glycerol

    1. Glycerol

    - propane-1,2,3-triol)- Physical data (molecular weight 92.11, melting point 20oC,

    density 1.2611 g/cm3, viscosity 1 759.6 cP, solubility in

    water/alcohol infinitely)

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    Fatty Acid

    o > 200 are known

    o Monocarbonic acid, usually derived from aliphatic hydrocarbon

    o The structure of fatty acid has a great influence on their physicaldata

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    Occurrence of Fatty Acids

    Saturated fatty acids (CnH2nO2)

    n Trivial name Occurrence in common oils and fats

    4 Butyric Milk fats (3 5)

    6 Caproic milk fat (2-3), coconut oil (

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    Fats and oils of plant origin

    Linseed oil : seed of the flax plant Linum usitatissimum, major constituentlinolenic acid, mainly used in the paint and varnish industry

    Tung Oil (China wood oil) : seed or nut of the tree Aleurites fordii and

    Aleurites montana, highly unsaturated oil (eleostearic acid), rapid dryingproperties

    Sunflower seed oil : major constituent linoleic and oleic acids

    Corn oil : oleic and linoleic acids

    Tomato seed oil : by product of tomato paste manufacture, oleic andlinoleic acids

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    Sesame oil : oleic and linoleic acids, high content of saponifiable mattersuch as sesamine and seasamoline (give distinctive color reaction)

    Cotton seed oil : high content of linoleic acid

    Safflower oil : seed of Carthamus tinctorius, linoleic acid, drying oil

    (intermediate characteristic between soybean and linseed oil)

    Soybean oil : high content of linoleic acid, the crude oil contains largeamount of non glyceride material (phosphatide)

    Rice bran oil : bran of Oryza sativa, contain large amount of non glyceridematerial and active lipase, the acidity (during storage) rises at the rate of 1%

    per hour

    Kapok oil : seed of Ceiba pentandra, palmitic, oleic and linoleic acids

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    Castor oil : seed of Ricinus communis, high acetyl or hydroxyl value, highspecific gravity, high viscosity, high solubility in glacial acetic acid, lowersolubility in petroleum solventhigh content of ricinoleic acid

    Palm oil : palmitic, oleic and linoleic acids

    Palm kernel oil : lauric and myristic acids

    Cocoa butter/cacao butter : bean of Theobroma cacao, has a specific odorand flavor, palmitic, stearic and oleic acids

    Coconut oil : has a specific odor, lauric and myristic acids

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    Fats of animal origin

    Hog (pig) fat or lard : bacon (subcutaneous fatty tissue), lard/hog fat (renderedfrom the internal tissues), palmitic, stearic and oleic acids

    Tallow : from the fatty tissues of cattle, sheep and goats, palmitic, stearic and

    oleic acids

    Sardine oil : from the body of the Caerulea and Ocelata sardinops, palmiticacid

    Cod liver oil : from the fish Gadus morrhua, high content of vit A and D

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    Physical PropertiesSpecific gravity/Density

    - the specific gravity increases along with increase in the degree ofunsaturation

    - the hydrogenation of fat lower their specific gravity

    Melting Point

    - the melting point of a fatty acid increases together with the increase in thechain length of the acids

    - the higher unsaturation degree of a substance the lower its melting point

    - the melting point of a triglyceride is related to that of the correspondingfatty acids

    - the melting point of a diglyceride is higher than that of the correspondingtriglyceride

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    Butyric acid -8Caproic acid -1

    Caprylic acid 16

    Capric acid 31.3

    Lauric acid 43.4

    Myristic acid 54.4

    Palmitic acid 62.9

    Stearic acid 69.6

    Oleic acid 16

    Elaidic acid 44Erucic acid 34

    Linoleic acid -7

    Linolenic acid -13

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    Boiling Point

    -the boiling point of fatty acids increases together with increase in their chainlength

    - the vapour pressure of a glyceride is always considerably lower than that of

    the corresponding fatty acidIodine Value : a measure for determining the unsaturation degree of fats andfatty acids, defined as the amount of iodine (in gram) which is absorbed by100 gram of fat

    Peroxide Value : a measure for determining the content of reactive oxygen

    of fats and oils in terms of milliequivalents of oxygen per 1000 gram fats, forevaluating their keeping qualities or shelf life.

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    Acid Value : a measure used for determining the content of free fatty acidscontained in oils/fats; defined as the number of milligrams of potassium

    hydroxide needed to neutralize the FFA contained in 1 gram of fat; the acidity

    of fats and oils is expressed in terms of %FFA; acid value : FFA = 1 : 0.503

    Saponification Value : the number of milligrams of potassium hydroxide

    needed to saponify 1 gram of fat.

    Acetyl Value : refers to the determination of the free hydroxyl groups

    contained in fats and oils; represented by the number of milligrams of

    potassium hydroxide needed to neutralize the acetic acid produced by

    splitting of 1 gram of acetylated fat

    Hydroxyl Value : the number of milligrams of potassium hydroxide required to

    neutralize the number of hydroxyls contained in 1 gram of fatty acids.

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    MINOR COMPONENTS OF FATS AND OILS

    Phosphatides

    glycerophosphatides

    sphyngolipids

    Unsaponifiables (the portion of oils and fats which is not saponified; varies0.5 2%)

    sterols (simply alicyclic alcohols)

    vitamins-tocopherols (vit A, D, E, K)

    waxes (the fatty acids present instead of being esterified with glycerol areesterified with a sterol or a aliphatic alcohol C26 C36)

    coloring substances

    aliphatic and terpenic alcohols

    saturated and unsaturated hydrocarbons

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    PURIFICATION OF FATS AND OILS

    SUBSTANCES MUST BE REMOVED :

    1. Solid impurities (solids or meal fines)

    The most serious troubles :- Formation of difficult to process sludge in storage tanks

    - Neutral oil losses during neutralization (fines act as emulsifier)

    - Slowing down of the processing cycle

    2. Mucilagenous materials, phosphatides, peroxides etc

    - Soy bean 1.5 3%

    - Rapeseed 1.5 2.5%

    - Maize 1 - 2%

    - Cottonseed 0.5 1.5%

    - Sunflower 0.5 1%

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    3. Volatile impurities (water, solvent, ether etc)

    4. Trace metals such as copper and iron (pro-oxidants)

    5. Pigments, primary and secondary oxidation products

    6. Waxes and unsaponifiables

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    Degumming with phosphoric acid Acid charred & precipitated (coagulated) proteins, phosphatides,

    gum Separation : settling & centrifugation Crude oil is heated to 70 80oC, mixed with acid solution (0.3

    0.4%, 15 20 minutes) Sulphuric acid : 66o Be, temp 30oC, high temp : partial sulphonation

    of oil (red color) Acid : phosphoric, oxalic, citric, sulphuric

    Water degumming (purification by hydration)

    Phosphatides, proteins & other colloidal impurities soluble in the oilonly in anhydrous form precipitated in the form of flocs of higher

    specific gravity

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    NEUTRALISATION OF FATS AND OILS

    Acidity of the oil : expressed as oleic acid (in general as this acid is present

    in all fats and oils)

    Source of acidity : fermentative process (special enzymes under condition

    of temperature split glycerides into glycerol and fatty acid.

    The glycerol decomposes, the free fatty acids remain dissolved in the oil

    and cause its acidity to rise.

    The most effective method to prevent : remove the maximum possible

    amount of water from the crude oilAcidity : neutral losses (split glyceride, neutral oil loss during neutralisation)

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    Factors :

    purity of fats and oils

    temperatures

    strength of alkaline solutions

    saponification time

    The most serious dangers : unusual losses of neutral oil, formation ofemulsions hindering soapstock separation, poor settling of soap flocs

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    In continuous operation

    Q = (Q1 x P x A x 1 000) / (100 x M x N)

    Q = quantity of NaOH solution (l/h)

    Q1 = quantity of oil (l/h)P = specific weight of oil

    A = acidity of the oil, expressed in percent

    M = molecular weight of fatty acid

    N = strength of NaOH, expressed as normalityExcess NaOH : 6% x Q

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    Average weight of fatty acid

    Coconut oil 205

    Palm kernel oil 214

    Palm oil 263

    Rapeseed oil 308

    Wesson loss (W%) = A + I

    A = % fatty acid

    I = % impurities

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    The limits of neutralisation losses

    FFA 4% = 1.4 x W%

    Strength of NaOH

    FFA < 1% : 8 12oBe

    FFA 1 6% : 20oBe

    FFA > 6% : > 20oBe

    Washing of oils after neutralisation : to remove the traces of soap, by the

    spraying water at a temperature of 90 95oC

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    Neutralisation by Saponification

    the reverse of fat hydrolysis/fat splitting

    conducted under vacuum, in the presence of an excess of glycerol and attemperature of 250oC, catalyst zinc or zinc chloride

    the weakness : occurrence of polymerisation, color change (to red) of theesterified product, deterioration of flavor

    Neutralisation by Distillation (Physical Refining)

    through distillation by injected steam to remove free fatty acid

    this process cant be applied to all oils :

    the oils are heated up to 220 250oC, oils undergo certain modification totheir molecular structure and consequently their chemical and physicalcharacteristic are modified

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    Neutralisation Via chemical Means

    Saponifying the free fatty acids present with aqueous solutions of sodiumhydroxide and seldom with others (potassium hydroxide, sodium carbonate)and in separating via physical means (settling and centrifugation)

    Reaction (reversible ~ temperature and pressure)Reactants : free fatty acid (R-COOH), NaOHProducts : soap (R-COONa), H2O

    The reaction is conducted at atmospheric pressure and medium temperature(60 80oC)

    Hydrolysis : high pressure (30 atm), high temperature

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    BLEACHING

    remove coloring matters (to be adsorbed by bleaching agent)

    bleaching agents : bleaching earth, activated carbon

    Bleaching Earths

    special clays activated by chemical or physical processes

    treatments : washing by sulphuric acid solution, filtration, drying, grinding

    adsorptive effect : surface tension, enhanced by the large surface area.

    the treatment of the clay is to remove the foreign matters contains in its

    capillary tubes so as to render it extremely porous and extend its surface.

    the mineral acid treatment increases the FFA content

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    ACTIVATED CARBON animal or plant origin

    plant origin : dry distillation of special tree branches

    the bleaching action : the large adsorbent surface of carbon held in small

    volume, would influence the surface tension of the compound with which it

    comes into contact, thus causing adsorption

    1 g carbon develop a surface area of several square meters

    common practice : mixture of activated carbon and bleaching earth in a

    ratio 5 10 % of carbon to 90 95 % of clay

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    Before being subjected to bleaching, fats/oils must be free of moisture. Theslightest traces of water in a fat may reduce the bleaching action of earthsand activated carbon

    Operation : heating the oil to a temperature range of 70 80oC under

    vacuum

    Temperature has a marked influence on the bleaching process every type of oil has its own optimum temperature (need preliminary teststo determine this optimum temperature)

    soy bean oil : 100oC

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    Time

    contact time has its influence on the decolorizing power of the adsorbent

    unique for every type of oil

    case : soybean oil

    o optimum contact time : 30 minuteso bleaching temperature : 95oC

    o amount of bleaching earth : 2%

    o absolute pressure : 60 mm Hg

    o agitation : vigorous

    Continuous process is more effective

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    Absolute pressure

    The surface area is made up by a countless number of capillary tubes,which in atmospheric ambient will become saturated with air (Thematerial must be deaerated)

    The simplest method : lowering the absolute pressure in the bleachingvessel to 50 70 mm Hg

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    Industrial Operation

    the bleacher is fed with a set amount of oil, temp 70 80oC under vacuum

    pressure (barometric condenser and vacuum pump)

    the agitator is operated until the moisture is completely removed

    after drying, a metered amount of bleaching agent is added and the

    temperature is raised to 100 110oC (contact time : 30 min)

    The suspension is pumped to the filtration section where the two

    components are separated

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    DEODORISATION to remove the compound which impart an unpleasant odor and flavor

    the compound (0.001 0.010%) : unsaturated carbohydrates, low

    molecular weight fatty acids (mainly butyric acid and caproic acid,

    aldehydes and ketones (formed during the various refining process)

    Great difference in volatility between odoriferous substances and

    glyceride

    Deodorisation : based on the higher volatile properties of odoriferous

    compounds (removed by distillation)

    Factors : temperature, pressure, time, material of deodoriser

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    The boiling point :

    Absolute pressure Palmitic acid Stearic acid Oleic acid

    (mm Hg) (oC) (oC) (oC)

    100 270 290 285

    40 244 263 255

    10 210 228 220

    4 192 209 205

    2 179 193 190

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    Optimum condition for operation :

    highest possible temperature

    lowest possible absolute pressure

    controlled amount of stripping steam

    An excessive increase in temperature may result in distillation of part ofthe glycerides, polymerisation and partial hydrolysis of the glycerides

    A prolonged deodorisation time has the following adverse results :polymerisation, cooked flavor of the oil, color deterioration of the refinedoil

    Deodorisation time : batch 5 12 hours, continue 1 3 hours

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    Type of oil Pressure (Torr) Temperature (oC)Soybean 10-20 200

    4-6 240

    Rapeseed 10-20 200

    4-6 240

    Coconut 10-20 180

    4-6 180

    Palm 10-20 180

    4-6 230

    Palm kernel 10-20 1804-6 230


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